Photoimageable polyolefin compositions containing photobase generators

ABSTRACT

Embodiments in accordance with the present invention encompass self-imageable polymer compositions containing a variety of photobase generators which are useful for forming films that can be patterned to create structures for microelectronic devices, microelectronic packaging, microelectromechanical systems, optoelectronic devices and displays. The compositions of this invention can be tailored to form positive tone or negative tone images depending upon the intended application in aqueous developable medium. The images formed therefrom exhibit improved properties including low wafer stress and better thermo-mechanical properties, among other property enhancements.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/918,604, filed Mar. 12, 2018, now allowed, which is a continuation ofU.S. application Ser. No. 15/042,240, filed Feb. 12, 2016, now U.S. Pat.No. 9,952,507 B1, issued, Apr. 24, 2018, which claims the benefit of U.S. Provisional Application No. 62/117,774, filed Feb. 18, 2015, all ofwhich are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally tophotoimageable compositions containing certain photobase generators(PBG) for forming microelectronic and/or optoelectronic devices andassemblies thereof, and more specifically to compositions encompassingpolymers derived from olefinic monomers, such as norbornene (NB) and/orstyrene, and maleic anhydride that are inexpensive yet exhibit improvedproperties, including low wafer stress and better thermo-mechanicalproperties.

Description of the Art

Organic polymer materials are increasingly being used in themicroelectronics and optoelectronics industries for a variety ofapplications. For example, the uses for such organic polymer materialsinclude interlevel dielectrics, redistribution layers (RDL), stressbuffer layers, chip stacking and/or bonding, leveling or planarizationlayers, alpha-particle barriers, passivation layers, among others, inthe fabrication of a variety of microelectronic and optoelectronicdevices. Where such organic polymer materials are photosensitive, thusself-imageable, and therefore, offer additional advantage of reducingthe number of processing steps required for the use of such layers andstructures made therefrom. Additionally, such organic polymer materialsenable the direct adhesive bonding of devices and device components toform various structures. Such devices include microelectromechanicalsystems (MEMS), microoptoelectromechanical systems (MOEMS) and thesemiconductor device encompassing a complementary metal oxidesemiconductor (CMOS) image sensor dam structure, and the like.

While certain of the currently available organic photosensitivecompositions are used in some of the aforementioned applications, thereis still a need for organic photosensitive compositions which areaqueous negative or positive tone developable especially in suchapplications as RDL, chip stacking/bonding and CMOS, where there is agrowing concern to avoid solvents as the increase demand in suchapplications has resulted in more solvent waste. At the same time anynew aqueous developable compositions should still feature same or betterproperties than the currently used solvent developable compositions. Inparticular, several of the current compositions utilize polymers such aspolyimide, benzocyclobutenes (BCB) and silicones are expensive, and someof which utilize solvents for developing.

Accordingly, there is still a need for lower cost aqueous developablenegative or positive tone compositions which feature better properties,such as for example, i) lower temperature curing which still maintainspattern integrity, ii) improved thermo-mechanical properties, iii)improved elongation to break (ETB), and iv) lower wafer stress, just toname a few.

SUMMARY OF THE INVENTION

It has now been found that by employing one or more photobase generators(TBG), it is now possible to fabricate a semiconductor device whichfeatures hitherto unachievable properties, i.e., improvedthermo-mechanical properties, improved elongation to break, and lowerwafer stress, yet can be readily integrated into conventionalapplications, such as for example, CMOS image sensor (CIS) applicationsor redistribution layer (RDL) applications, and the like.

Accordingly, there is provided a photoimageable compositionencompassing:

a) a polymer having one or more first type of repeating unitsrepresented by formula (IA), said first type of repeating unit isderived from a monomer of formula (I):

wherein:

m is an integer 0, 1 or 2;

R₁, R₂, R₃ and R₄ are the same or different and each independentlyrepresents hydrogen, halogen, a hydrocarbyl or halohydrocarbyl groupselected from linear or branched (C₁-C₁₂)alkyl, hydroxy(C₁-C₁₂)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₅-C₁₀)heteroaryl, (C₅-C₁₀)heteroaryl(C₁-C₃)alkyl, hydroxy,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl,(C₅-C₁₀)heteroaryloxy(C₁-C₃)alkyl, (C₆-C₁₀)aryloxy,(C₅-C₁₀)heteroaryloxy, (C₁-C₆)acyloxy, —(CH₂)_(a)—C(CF₃)₂OR,—(CH₂)_(a)—CO₂R,

a group of formula (A):—(CH₂)_(b)—(OCH₂—CH₂)_(c)—OR  (A); and

a group of formula (B):

wherein:

a is an integer from 0 to 4

b is an integer from 0 to 10;

c is an integer 0, 1, 2, 3 or 4; and

R is hydrogen, linear or branched (C₁-C₆)alkyl, (C₅-C₈)cycloalkyl,(C₆-C₁₀)aryl or (C₇-C₁₂)aralkyl;

and/or

a second type of repeating unit represented by formula (IIA), saidsecond type of repeating unit is derived from a monomer of formula (II):

wherein

R₈, R₉, R₁₀ and R₁₁ are the same or different and each independently ofone another is selected from hydrogen, linear or branched (C₁-C₆)alkyl,(C₅-C₈)cycloalkyl, (C₆-C₁₀)aryl and (C₇-C₁₂)aralkyl; and

a third type of repeating unit represented by formula (IIIA) or (IIIB),said second type of repeating unit is derived from a monomer of formula(III):

wherein:

Z is O or N—R₁₂ wherein R₁₂ is hydrogen, linear or branched(C₁-C₉)alkyl, (C₃-C₇)cycloalkyl and (C₆-C₁₂)aryl;

R₅, R₆ and R₇ are each independently of one another selected fromhydrogen, linear or branched (C₁-C₉)alkyl, fluorinated orperfluorinated(C₁-C₉)alkyl, (C₆-C₁₂)aryl and (C₆-C₁₂)aryl(C₁-C₁₂)alkyl;and

wherein each of aforementioned groups, where valence is permissible, isoptionally substituted with one or more groups selected from linear orbranched (C₁-C₆)alkyl, (C₃-C₇)cycloalkyl, (C₁-C₆)perfluoroalkyl,(C₁-C₆)alkoxy, (C₃-C₇)cycloalkoxy, (C₁-C₆)perfluoroalkoxy, halogen,hydroxy, linear or branched hydroxy(C₁-C₆)alkyl, acetoxy, phenyl,hydroxyphenyl and acetoxyphenyl;

b) a photobase generator; and

d) a carrier solvent.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments in accordance with the present invention are described belowwith reference to the following accompanying figures and/or images.Where drawings are provided, it will be drawings which are simplifiedportions of various embodiments of this invention and are provided forillustrative purposes only.

FIG. 1 shows the scanning electron micrograph (SEM) of a negative tonephoto image formed from a composition embodiment of this invention.

FIG. 2 shows another SEM of a positive tone photo image formed from acomposition embodiment of this invention.

FIGS. 3A to 3C show the SEM micrographs of a cross section of 75 μm viasobtained with a composition embodiment of this invention.

FIGS. 4A to 4C show the SEM micrographs of a cross section of 75 μm viasobtained with another composition embodiment of this invention.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the symbol “

” denotes a position at which the bonding takes place with anotherrepeat unit or another atom or molecule or group or moiety asappropriate with the structure of the group as shown.

As used herein, “hydrocarbyl” refers to a group that contains carbon andhydrogen atoms, non-limiting examples being alkyl, cycloalkyl, aryl,aralkyl, alkaryl, and alkenyl. The term “halohydrocarbyl” refers to ahydrocarbyl group where at least one hydrogen has been replaced by ahalogen. The term perhalocarbyl refers to a hydrocarbyl group where allhydrogens have been replaced by a halogen.

As used herein, the expression “(C₁-C₆)alkyl” includes methyl and ethylgroups, and straight-chained or branched propyl, butyl, pentyl and hexylgroups. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyland tert-butyl. Derived expressions such as “(C₁-C₄)alkoxy”,“(C₁-C₄)thioalkyl”, “(C₁-C₄)alkoxy(C₁-C₄)alkyl”, “hydroxy(C₁-C₄)alkyl”,“(C₁-C₄)alkylcarbonyl”, “(C₁-C₄)alkoxycarbonyl(C₁-C₄)alkyl”,“(C₁-C₄)alkoxycarbonyl”, “amino(C₁-C₄)alkyl”, “(C₁-C₄)alkylamino”,“(C₁-C₄)alkylcarbamoyl(C₁-C₄)alkyl”,“(C₁-C₄)dialkylcarbamoyl(C₁-C₄)alkyl”, “mono- ordi-(C₁-C₄)alkylamino(C₁-C₄)alkyl”, “amino(C₁-C₄)alkylcarbonyl”,“diphenyl(C₁-C₄)alkyl”, “phenyl(C₁-C₄)alkyl”,“phenylcarbonyl(C₁-C₄)alkyl” and “phenoxy(C₁-C₄)alkyl” are to beconstrued accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “(C₂-C₆)alkenyl” includes ethenyl andstraight-chained or branched propenyl, butenyl, pentenyl and hexenylgroups. Similarly, the expression “(C₂-C₆)alkynyl” includes ethynyl andpropynyl, and straight-chained or branched butynyl, pentynyl and hexynylgroups.

As used herein the expression “(C₁-C₄)acyl” shall have the same meaningas “(C₁-C₄)alkanoyl”, which can also be represented structurally as“R—CO—,” where R is a (C₁-C₃)alkyl as defined herein. Additionally,“(C₁-C₃)alkylcarbonyl” shall mean same as (C₁-C₄)acyl. Specifically,“(C₁-C₄)acyl” shall mean formyl, acetyl or ethanoyl, propanoyl,n-butanoyl, etc. Derived expressions such as “(C₁-C₄)acyloxy” and“(C₁-C₄)acyloxyalkyl” are to be construed accordingly.

As used herein, the expression “(C₁-C₆)perfluoroalkyl” means that all ofthe hydrogen atoms in said alkyl group are replaced with fluorine atoms.Illustrative examples include trifluoromethyl and pentafluoroethyl, andstraight-chained or branched heptafluoropropyl, nonafluorobutyl,undecafluoropentyl and tridecafluorohexyl groups. Derived expression,“(C₁-C₆)perfluoroalkoxy”, is to be construed accordingly. It shouldfurther be noted that certain of the alkyl groups as described herein,such as for example, “(C₁-C₆)alkyl” may partially be fluorinated, thatis, only portions of the hydrogen atoms in said alkyl group are replacedwith fluorine atoms and shall be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl” means substituted orunsubstituted phenyl or naphthyl. Specific examples of substitutedphenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl,1-methylnaphthyl, 2-methylnaphthyl, etc. “Substituted phenyl” or“substituted naphthyl” also include any of the possible substituents asfurther defined herein or one known in the art. Derived expression,“(C₆-C₁₀)arylsulfonyl,” is to be construed accordingly.

As used herein, the expression “(C₆-C₁₀)aryl(C₁-C₄)alkyl” means that the(C₆-C₁₀)aryl as defined herein is further attached to (C₁-C₄)alkyl asdefined herein. Representative examples include benzyl, phenylethyl,2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “heteroaryl” includes all of the knownheteroatom containing aromatic radicals. Representative 5-memberedheteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl,isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl,and the like. Representative 6-membered heteroaryl radicals includepyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the likeradicals. Representative examples of bicyclic heteroaryl radicalsinclude, benzofuranyl, benzothiophenyl, indolyl, quinolinyl,isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl,pyridothienyl, and the like radicals.

As used herein, the expression “heterocycle” includes all of the knownreduced heteroatom containing cyclic radicals. Representative 5-memberedheterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl,pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl,and the like. Representative 6-membered heterocycle radicals includepiperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like.Various other heterocycle radicals include, without limitation,aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hept-2-yl, andtriazocanyl, and the like.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of C₁₋₆alkyl, C₂₋₆alkenyl, C₁₋₆perfluoroalkyl,phenyl, hydroxy, —CO₂H, an ester, an amide, C₁-C₆alkoxy, C₁-C₆thioalkyl,C₁-C₆perfluoroalkoxy, —NH₂, Cl, Br, I, F, —NH-lower alkyl, and —N(loweralkyl)₂. However, any of the other suitable substituents known to oneskilled in the art can also be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

It will be understood that, as used herein, the phrase “microelectronicdevice” is inclusive of a “micro-optoelectronic device” and an“optoelectronic device”. Thus, reference to microelectronic devices or amicroelectronic device assemblies are inclusive of optoelectronicdevices and micro-optoelectronic devices as well as assemblies thereof.Similarly, microelectromechanical systems (MEMS) includemicrooptoelectro-mechanical systems (MOEMS).

It will be understood that the term “redistribution layer (RDL)” refersto an electrical signal routing insulation material which featuresdesirable and reliable properties. The term RDL may also be usedinterchangeably to describe buffer coating layers, such as for example,a stress relief or buffer layer between the solder ball and fragilelow-K structure.

As used herein, the terms “polymer composition,” “copolymercomposition,” “terpolymer composition” or “tetrapolymer composition” areused herein interchangeably and are meant to include at least onesynthesized polymer, copolymer, terpolymer or tetrapolymer, as well asresidues from initiators, solvents or other elements attendant to thesynthesis of such polymers, where such residues are understood as notnecessarily being covalently incorporated thereto. But some catalysts orinitiators may sometimes be covalently bound to a part of the polymericchain either at the beginning and/or end of the polymeric chain. Suchresidues and other elements considered as part of the “polymer” or“polymer composition” are typically mixed or co-mingled with the polymersuch that they tend to remain therewith when it is transferred betweenvessels or between solvent or dispersion media. A polymer compositioncan also include materials added after synthesis of the polymer toprovide or modify specific properties of such composition. Suchmaterials include, but are not limited to solvent(s), antioxidant(s),photoinitiator(s), sensitizers and other materials as will be discussedmore fully below.

As used herein, the term “modulus” is understood to mean the ratio ofstress to strain and unless otherwise indicated, refers to the Young'sModulus or Tensile Modulus measured in the linear elastic region of thestress-strain curve. Modulus values are generally measured in accordancewith ASTM method DI708-95. Films having a low modulus are understood toalso have low internal stress.

The term “photodefinable” refers to the characteristic of a material orcomposition of materials, such as a polymer or polymer composition inaccordance with embodiments of the present invention, to be formed into,in and of itself, a patterned layer or a structure. In alternatelanguage, a “photodefinable layer” does not require the use of anothermaterial layer formed thereover, for example, a photoresist layer, toform the aforementioned patterned layer or structure. It will be furtherunderstood that a polymer composition having such a characteristic isgenerally employed in a pattern forming scheme to form a patternedfilm/layer or structure. It will be noted that such a schemeincorporates an “imagewise exposure” of the photodefinable material orlayer formed therefrom. Such imagewise exposure being taken to mean anexposure to actinic radiation of selected portions of the layer, wherenon-selected portions are protected from such exposure to actinicradiation.

As used herein, the term “self-imageable compositions” will beunderstood to mean a material that is photodefinable and can thusprovide patterned layers and/or structures after direct image-wiseexposure of a film formed thereof followed by development of such imagesin the film using an appropriate developer.

It will be understood that the terms “dielectric” and “insulating” areused interchangeably herein. Thus reference to an insulating material orlayer is inclusive of a dielectric material or layer and vice versa.Further, as used herein, the term “organic electronic device” will beunderstood to be inclusive of the term “organic semiconductor device”and the several specific implementations of such devices such as theorganic field effect transistors (OFETs).

As used herein, the term “photobase generator” (PBG) and similar terms,such as, “photo activated base generator” and “photo initiator” meansany material which when exposed to suitable radiation generates one ormore bases.

By the term “derived” is meant that the polymeric repeating units arepolymerized (formed) from, for example, polycyclic norbornene-typemonomers (or the olefinic monomers of formula (II)), in accordance withformulae (I) or maleic anhydride type monomers of formula (III) whereinthe resulting polymers are formed by 2,3 enchainment of norbornene-typemonomers with maleic anhydride type monomers in an alternating fashionas shown below:

It should be understood that depending upon the monomeric compositionsin a given polymer the repeat units may not always be alternating. Thatis to say, for example, in a copolymer containing other than 50:50 molarratios of norbornene-type monomers with maleic anhydride monomers, therepeat units are not always alternating but with random blocks ofmonomers with the higher molar content.

Accordingly, in accordance with the practice of this invention there isprovided photoimageable composition encompassing:

-   -   a) a polymer having one or more first type of repeating units        represented by formula (IA), said first type of repeating unit        is derived from a monomer of formula (I):

wherein:

m is an integer 0, 1 or 2;

R₁, R₂, R₃ and R₄ are the same or different and each independentlyrepresents hydrogen, halogen, a hydrocarbyl or halohydrocarbyl groupselected from linear or branched (C₁-C₁₂)alkyl, hydroxy(C₁-C₁₂)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl,(C₅-C₁₀)heteroaryl, (C₅-C₁₀)heteroaryl(C₁-C₃)alkyl, hydroxy,(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,(C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy(C₁-C₃)alkyl,(C₅-C₁₀)heteroaryloxy(C₁-C₃)alkyl, (C₆-C₁₀)aryloxy,(C₅-C₁₀)heteroaryloxy, (C₁-C₆)acyloxy, —(CH₂)_(a)—C(CF₃)₂OR,—(CH₂)_(a)—CO₂R,

a group of formula (A):(CH₂)_(b)—(OCH₂—CH₂)_(c)—OR  (A); and

a group of formula (B):

wherein:

a is an integer from 0 to 4

b is an integer from 0 to 10;

c is an integer 0, 1, 2, 3 or 4; and

R is hydrogen, linear or branched (C₁-C₆)alkyl, (C₅-C₈)cycloalkyl,(C₆-C₁₀)aryl or (C₇-C₁₂)aralkyl;

and/or

a second type of repeating unit represented by formula (IIA), saidsecond type of repeating unit is derived from a monomer of formula (II):

wherein

R₈, R₉, R₁₀ and R₁₁ are the same or different and each independently ofone another is selected from hydrogen, linear or branched (C₁-C₆)alkyl,(C₅-C₈)cycloalkyl, (C₆-C₁₀)aryl and (C₇-C₁₂)aralkyl; and

a third type of repeating unit represented by formula (IIIA) or (IIIB),said second type of repeating unit is derived from a monomer of formula(III):

wherein:

Z is O or N—R₁₂ wherein R₁₂ is hydrogen or linear or branched(C₁-C₉)alkyl, (C₃-C₇)cycloalkyl and (C₆-C₁₂)aryl;

R₅, R₆ and R₇ are each independently of one another selected fromhydrogen, linear or branched (C₁-C₉)alkyl, fluorinated orperfluorinated(C₁-C₉)alkyl, (C₆-C₁₂)aryl and (C₆-C₁₂)aryl(C₁-C₁₂)alkyl;and

wherein each of aforementioned groups, where valence is permissible, isoptionally substituted with one or more groups selected from linear orbranched (C₁-C₆)alkyl, (C₃-C₇)cycloalkyl, (C₁-C₆)perfluoroalkyl,(C₁-C₆)alkoxy, (C₃-C₇)cycloalkoxy, (C₁-C₆)perfluoroalkoxy, halogen,hydroxy, linear or branched hydroxy(C₁-C₆)alkyl, acetoxy, phenyl,hydroxyphenyl and acetoxyphenyl;

-   -   b) a photobase generator; and    -   d) a carrier solvent.

The polymers employed in the photoimageable compositions of thisinvention can be synthesized by any of the procedures known to oneskilled in the art. Generally, such polymers are prepared by freeradical polymerization. See for example, U.S. Pat. No. 8,715,900, whichdiscloses ring-opened maleic anhydride polymers with alcohols (ROMA) andcopolymerized with a variety of norbornene monomers as described herein,pertinent portions of which are incorporated herein by reference. Also,see copending U.S. patent application Ser. No. 14/477,928, filed Sep. 5,2014, which further discloses various ring-opened maleic anhydridepolymers with amines (ROMI) and copolymerized with a variety ofnorbornene monomers as described herein, pertinent portions of which areincorporated herein by reference. Various other types of polymerscontaining norbornene repeat units as employed herein can also beprepared by vinyl addition polymerization using transition metalcatalysts, such as for example, nickel or palladium. See for example,U.S. Pat. Nos. 5,929,181; 6,455,650; 6,825,307; and 7,101,654; pertinentportions of which are incorporated herein by reference.

In general, the polymer embodiments in accordance with the presentinvention encompass the above described one or more of the firstdistinct type of repeating units of formula (IA) in combination with therepeating unit of formula (IIIA) or (IIIB), as it will be seen below,various repeating units encompassed by such polymer embodiments areselected to provide properties to such polymer embodiments that areappropriate and desirable for the use for which such embodiments aredirected, thus such polymer embodiments are tailorable to a variety ofspecific applications.

For example, polymer embodiments generally require at least onerepeating unit directed to providing imageability. Thus distinct typesof repeating units, represented by structural formula (IA) can be usedas defined hereinabove, such as, for example R₁ being a phenethyl group.However, any of the other functional group which would bring aboutsimilar result can also be used instead, for example, a phenyl, benzylor a substituted phenyl, and the like. Furthermore, the repeat units offormula (IIIA), which contains a carboxylic acid pendent group aregenerally useful for participating in a reaction with appropriatelyselected additives, or other repeating units that can lead to fix anegative-tone image during exposure to a suitable radiation and furthercured by post exposure baking conditions as further explained below.Advantageously, same composition can also be used for fixing apositive-tone image post exposure thermal crosslinking as furtherexplained below. It should further be noted that one of skill in the artreadily appreciates that such polymer compositions containing acidicpendent groups can be made post polymerization by utilizing appropriatemonomers. For example, a copolymer containing repeat units of formula(IIIB) are formed first, which is subsequently reacted with suitablealcohol or amine to form the copolymers containing the carboxylic acidpendent groups by any of the known procedures in the art. Thus certainresidual amount of the anhydride monomeric repeat units of formula(IIIB) may always be present in the polymer employed herein.

Advantageously, it has further been found that the polymers employed inthe compositions of this invention can also contain a second type ofrepeat units of formula (IIA) along with repeat units of formula (IA)and in combination with repeat units of formula (IIIA) and (IIIB). Insome embodiments, the polymers of this invention contain only repeatunits of formula (IA) in combination with repeat units of formula (IIIA)and (IIIB). In some other embodiments, the polymers of this inventioncontain only repeat units of formula (IIA) in combination with repeatunits of formula (IIIA) and (IIIB). Accordingly, all such combinationsof repeat units are within the scope of this invention.

In general, the polymers employed herein are copolymers containing 50:50molar ratio of repeat units of formula (IA) or repeat units of formula(IIA) and a combination of repeat units of formula (IIIA) and (IIIB).However, in some embodiments the polymers of this invention may contain50:50 molar ratio of combination of repeat units of formula (IA) and(IIA) in combination with repeat units of formula (IIIA) and (IIIB).That is to say that, generally, the polymer encompasses equal moles ofrepeat units of formula (IA) or (IIA) and combined repeat units offormulae (IIA) and (IIB). In other words, when more than one type ofnorbornene monomers are used to make the polymer used in the compositionembodiment of this invention, then the total moles of the norbornenederived repeat units are same as the total moles of the maleic anhydridederived repeat units (i.e., combined moles of formulae (IIIA) and(IIIB). Similarly, when more than one type of monomers of formula (II)are used to make the polymer used in the composition embodiment of thisinvention, then the total moles of the derived repeat units of formula(IIA) are same as the total moles of the maleic anhydride derived repeatunits (i.e., combined moles of formulae (IIIA) and (IIIB). Thus,generally, the polymers employed herein feature alternating repeat unitsof norbornene (or other olefinic repeat unit of formula (IIA) and maleicanhydride units. However, it is also possible that more molar ratios ofnorbornene type units can be employed to make certain polymers where theexcess norbornene repeat units may exist together, such as for example,polymers containing 60:40, 70:30 or 80:20 mole ratio of norbornene tomaleic anhydride. Similarly, it is also possible that there may beexcess maleic anhydride derived repeat units, such as for example,40:60, 30:70 or 20:80 mole ratio of norbornene to maleic anhydride. Allsuch combination of polymers can be employed in the composition of thisinvention.

In general, it has now been found that a polymer containing the monomerrepeat unit having an acidic pendent group (generally of formula (IIIA),where Z is O and R₇ is hydrogen or Z is N—R₁₂ and R₇ is hydrogen)advantageously provides certain beneficial effect for the photosensitivecomposition of this invention. Thus, in some embodiments of thisinvention, the polymer used in the photosensitive composition of thisinvention contains a monomer repeat unit containing the acid pendentgroup from about 10 to 50 mol %, and in some other embodiments from 20to 40 mol %. In some other embodiments the molar percent of the monomerrepeat units of formula (IIIA), where Z is O and R₇ is hydrogen (thatmeans completely ring opened and hydrolyzed), in the polymer may be fromabout 10 to 50 mol %, from about 20 to 45 mol % and in some otherembodiments from about 30 to 40 mol %. In some other embodiments themolar percent of norbornene type monomer repeat units of formula (IA) inthe polymer may be from about 50 to 60 mol %.

Accordingly, any of the known monomers of formula (I) can be employed inthis aspect of the invention. Representative examples of monomers offormula (I) include the following without any limitations:

Turning now to second repeating unit of formula (IIA) to form thepolymer for use in the composition of this invention it is contemplatedthat any monomer of formula (II) can be employed. Exemplary monomers ofsuch type include but not limited to those selected from the groupconsisting of:

-   2-methylprop-1-ene;-   2-methylpent-1-ene;-   2,4,4-trimethylpent-1-ene;-   2,4,4-trimethylpent-2-ene;-   trimethyl(vinyl)silane;-   styrene; and-   α-methylstyrenre.

Turning now to third repeating unit of formula (IIIA) or (IIIB) to formthe polymer for use in the composition of this invention it iscontemplated that any maleic anhydride derivative can be used as amonomer, including maleic anhydride itself. Exemplary monomers of suchtype include but not limited to those selected from the group consistingof:

In a further embodiment, the composition of this invention encompasses apolymer which is a copolymer or a terpolymer containing one or moremonomers of formula (I) and at least one monomer of formula (III), whichresults in repeat units of formula (IIIA) or (IIIB).

In another embodiment, the composition of this invention encompasses apolymer which is a copolymer or a terpolymer containing one or moremonomers of formula (II) and at least one monomer of formula (III),which results in repeat units of formula (IIIA) or (IIIB).

In yet a further embodiment, the composition of this inventionencompasses a polymer containing one or more monomers of formula (I),one or more monomers of formula (II) and at least one monomer of formula(III), which results in repeat units of formula (IIIA) or (IIIB).

In another embodiment the composition of this invention encompasses apolymer wherein Z is O, R₅ and R₆ are hydrogen, and R₇ is hydrogen orlinear or branched (C₁-C₉)alkyl. That is to say that in such embodimentsthe polymer employed is derived from a maleic anhydride monomer which isring opened with any of the (C₁-C₉)alcohols, including methanol,ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, tert-butanol,n-pentanol, n-hexanol, n-heptyl alcohol, n-octyl alcohol, n-nonylalcohol, and the like. However, it should be noted that any of thehigher alcohols, including the cyclic alcohols can also be employed.

In another embodiment the composition of this invention encompasses apolymer wherein Z is N—R₁₂, R₅ and R₆ are hydrogen, R₇ is hydrogen andR₁₂ is hydrogen or linear or branched (C₁-C₉)alkyl. That is to say thatin such embodiments the polymer employed is derived from a maleicanhydride monomer which is ring opened with any of the (C₁-C₉)alkylamines, including methyl amine, ethyl amine, n-propyl amine, isopropylamine, n-butyl amine, iso-butyl amine, tert-butyl amine, n-pentyl amine,n-hexyl amine, n-heptyl amine, n-octyl amine, n-nonyl amine, and thelike.

In another embodiment, the composition of this invention encompasses apolymer derived from a monomer of formula (I) wherein m is 0, R₁, R₂, R₃and R₄ independently represents hydrogen, hexyl, decyl,—(CH₂)₂—C(CF₃)₂OH, —(CH₂)₂—CO₂H, benzyl and phenethyl.

Again, any of the polymerizable monomer as described herein can be used.Thus, in one of the embodiments the polymer of this inventionencompasses one or more repeat units derived from the correspondingmonomers selected from the group consisting of:

-   bicyclo[2.2.1]hept-2-ene (NB)-   5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);-   5-octylbicyclo[2.2.1]hept-2-ene (OctNB);-   5-decylbicyclo[2.2.1]hept-2-ene (DecNB);-   norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);-   5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C₄F₉NB);-   tetraoxadodecanenorbornene (NBTODD);-   5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM);-   5-(3-methoxypropanoxy)methyl-2-norbornene (NB-3-MPM);-   5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene    (NBTON);-   2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)oxirane (MGENB);-   2-(bicyclo[2.2.1]hept-5-en-2-yl)oxirane; and-   2-(7-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)oxirane.-   5-benzylbicyclo[2.2.1]hept-2-ene (BenNB);-   5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);-   ethyl 3-(bicyclo[2.2.1]hept-2-en-2-yl)propanoate (EPEsNB),-   bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (Acid NB) and-   norbornenylpropanoic acid (NBEtCOOH).

In yet another embodiment the polymer of this invention encompasses oneor more repeat units derived from the corresponding monomers of formula(I) selected from the group consisting of:

-   bicyclo[2.2.1]hept-2-ene (NB);-   5-decylbicyclo[2.2.1]hept-2-ene (DecNB);-   norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);-   5-phenethylbicyclo[2.2.1]hept-2-ene (PENB); and-   norbornenylpropanoic acid (NBEtCOOH).

In yet another embodiment of this invention, the composition encompassesa polymer having one or more repeat units derived from the correspondingmonomers of formula (II) selected from the group consisting of:

-   styrene; and-   α-methylstyrene.

In a further embodiment of this invention, the composition encompasses apolymer having one or more repeat units derived from the correspondingmonomers of formula (III) selected from the group consisting of:

-   maleic anhydride; and-   2-methyl-maleic anhydride.

Non-limiting examples of such copolymers or terpolymers include:

a copolymer containing repeating units derived from5-phenethylbicyclo[2.2.1]hept-2-ene (PENB) and fully ring opened maleicanhydride repeat unit of formula (IIIA), which is ring opened withmethanol, i.e., where R₅ and R₆ are hydrogen, Z is O and R₇ is methyl;

a copolymer containing repeating units derived frombicyclo[2.2.1]hept-2-ene (NB) and fully ring opened maleic anhydriderepeat unit of formula (IIIA), which is ring opened with n-butanol,i.e., where R₅ and R₆ are hydrogen, Z is O and R₇ is n-butyl;

a terpolymer containing repeating units derived from5-phenethylbicyclo[2.2.1]hept-2-ene (PENB),5-decylbicyclo[2.2.1]hept-2-ene (DecNB) and fully ring opened maleicanhydride repeat unit of formula (IIIA), which is ring opened withmethanol, i.e., where R₅ and R₆ are hydrogen, Z is O and R₇ is methyl;and

a copolymer containing repeating units derived from styrene and fullyring opened maleic anhydride repeat unit of formula (IIIA), which isring opened with n-butylamine, i.e., where R₅ and R₆ are hydrogen, Z isN-n-butyl and R₇ is hydrogen.

The polymers employed to form the compositions of this inventiongenerally exhibit a number average molecular weight (M_(w)) of at leastabout 2,000. In general, the polymers as described herein made inaccordance with the free radical polymerization exhibit lower molecularweight when compared with the polymers made in accordance with the vinyladdition polymerization methods. Accordingly, in another embodiment, thepolymer employed in the composition of this invention has a M_(w) of atleast about 5,000. In yet another embodiment, the polymer employed inthe composition of this invention has a M_(w) of at least about 8,000.In some other embodiments, the polymer of this invention has a M_(w) ofat least about 10,000. In some other embodiments, the polymer of thisinvention has a M_(w) ranging from about 20,000 to 50,000. In some otherembodiments, especially where the polymer is made by the procedures ofvinyl addition polymerization techniques, the polymer of this inventionhas a M_(w) of at least about 10,000. In some other embodiments, suchvinyl addition polymers employed in this invention has a M_(w) rangingfrom about 50,000 to 500,000. The weight average molecular weight(M_(w)) of the polymer can be determined by any of the known techniques,such as for example, by gel permeation chromatography (GPC) equippedwith suitable detector and calibration standards, such as differentialrefractive index detector calibrated with narrow-distributionpolystyrene standards.

Advantageously, the photobase generator used in the compositionembodiments in accordance with the present invention, generates a baseupon exposure to suitable radiation, where the generated base causescrosslinking of the polymer by itself or with other additives, such ascrosslinking agents as further described hereinbelow, thereby causingthe images to fix.

Accordingly, any of the known photobase generators can be employed inthe compositions of this invention which would bring about the aboveintended change. Broadly, such examples of photobase generators includewithout any limitation various carbamates that decompose upon exposureto suitable radiation releasing an amine, and various amine derivativesand suitable amine salts, among others. Other photobase generators thatcan be employed include a carboxylic acid or a functional equivalentderivative thereof of an amine or its equivalent, which when exposed toa suitable radiation decomposes to release the free base. All of suchcompounds as single component or mixtures in any combination thereof canbe used in the composition of this invention.

Illustrative examples of such photobase generators, without anylimitation may be enumerated as follows.

a compound of formula (IV):

a compound of formula (V):

a compound of formula (VI):

a compound of the formula (VIIA), (VIIB) or (VIIC):

wherein

R₁₃ and R₁₄ each independently of each other selected from hydrogen,linear or branched (C₁-C₈)alkyl and (C₆-C₁₀)aryl, or R₁₃ and R₁₄ takentogether with the nitrogen atom to which they are attached form a 5 to 7membered monocyclic ring or 6 to 12 membered bicyclic ring, said ringoptionally containing one or more heteroatoms selected from O and N, andsaid ring optionally substituted with linear or branched (C₁-C₈)alkyl,(C₆-C₁₀)aryl, halogen, hydroxy, linear or branched (C₁-C₈)alkoxy and(C₆-C₁₀)aryloxy; and

R₁₅, R₁₆ and R₁₇ are the same or different and each independently of oneanother is selected from hydrogen, linear or branched (C₁-C₁₆)alkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, hydroxy, halogen, linear orbranched (C₁-C₁₂)alkoxy and (C₆-C₁₀)aryloxy.

As defined herein R₁₃ and R₁₄ taken together with the nitrogen atom towhich they are attached form a 5 to 7 membered monocyclic ring or 6 to12 membered bicyclic ring in any of the aforementioned compounds offormulae (IV) to (VI). Such 5 to 7 membered monocyclic rings or 6 to 12membered bicyclic rings include any of the known “heteroaryl” or“heterocycle” rings as particularly defined hereinabove without anylimitation.

In some embodiments the composition of this invention encompasses aphotobase generator of formula (IV) wherein R₁₃ and R₁₄ areindependently of each other hydrogen, methyl or ethyl, R₁₅ is hydrogen,methyl or ethyl, and R₁₆ and R₁₇ are independently of each otherhydrogen, methyl and ethyl.

Specific examples of the photobase generators within the scope ofcompounds of formula (IV), (V), (VI), including specific compounds(VIIA), (VIIB) and (VIIC), that can be employed in the compositionembodiments of this invention are selected from the following groupwithout any limitation:

3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]primidin-1-ium2-(3-benzoylphenyl)propanoate (VIIA), also known as1,5,7-triaza-bicyclo[4.4.0]dec-5-enium 2-(3-benzoylphenyl)propanoate(commercially available as PT-393);

diaminomethaniminium 2-(3-benzoylphenyl)propanoate (VIIB), also known asguanidinium 2-(3-benzoylphenyl)propionate, commercially available asWPBG-82 from Wako Pure Chemical Industries, Ltd., Japan; and

(Z)—N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propan-2-aminium2-(3-benzoylphenyl)propanoate (VIIC), commercially available as WPBG-266from Wako Pure Chemical Industries, Ltd., Japan.

Various other known PBGs can also be used in the compositions of thisinvention which bring about the desirable change upon exposure tosuitable radiation, such as ultraviolet or visible radiation. Suchfurther examples of PBGs include α-amino acetophenone compound, an oximeester compound and a compound having a substituent such as anacyloxyimino group, a N-formylated aromatic amino group, a N-acylatedaromatic amino group, a nitrobenzylcarbamate group and analkoxybenzylcarbamate group. Specific examples of such PBGs may furtherinclude 9-anthrylmethyl N,N′-diethylcarbamate (available commercially asWPBG-018 from Wako Pure Chemical Industries, Ltd., Japan) and(E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine (availablecommercially as WPBG-027 from Wako Pure Chemical Industries, Ltd.,Japan).

The amount of PBG useful in composition embodiments in accordance withthe present invention is any amount that generates an effective amountof base to initiate the crosslinking reaction, such amount can thus bereferred to as an effective amount. For some embodiments, such amount isfrom 2 to 15 pphr inclusive, based on the weight of the polymer; inother embodiments from 4 to 10 pphr inclusive and in still otherembodiments, from 6 to 8 pphr inclusive. It will be understood, that forsome embodiments of the present invention, it can be advantageous toemploy a mixture of PBGs where the effective amount of such mixture isinclusive of the ranges expressed above.

Any of the solvents that can dissolve all of the components of thecomposition of this invention can be used as a carrier solvent.Representative examples of such solvents include alcohols, such asethanol, isopropanol, butanols, and the like. Ketone solvents, such asacetone, methyl ethyl ketone (MEK), methyl amyl ketone (MAK),cyclohexanone, cyclopentanone, and the like. Hydrocarbon solvents, suchas decane, toluene, p-menthane, and the like. Ester solvents, such asbenzyl acetate, ethyl acetate, and the like. Glycol and ether solvents,such as diethylene glycol dimethyl ether, propylene glycol monomethylether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and thelike. Various other solvents, such as N-methyl-2-pyrrolidone (NMP),gamma-butyrolactone (GBL), N,N-dimethylacetamide, N,N-dimethylformamide(DMF), anisole, methyl 3-methoxypropionate, tetrahydrofuran (THF),3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane(HFE-7500), 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane,1,1,1,2,2,3,4,4,4-nonafluoro-3-methoxybutane and mixtures in anycombination thereof.

As noted, PBGs generally absorb actinic radiation over a broad range ofwavelengths while in modern photoexposure tools, a limited range ofwavelengths or even a single wavelength, is provided. Therefore, inaddition to a PBG, a photosensitizer can be included within the polymercomposition where such material is selected to be absorbing at awavelength(s) used for the image-wise exposure. While any appropriatephotosensitizer can be employed, a useful photosensitizer for exposureat wavelengths that include 248 nanometers includes CPTX of the formula:

In addition, various other additives/components can be added to thecomposition of this invention, which is used for the formation of thephotoimageable layer such that its mechanical and other properties canbe tailored as desired. Also, other additives can be used to alter theprocessability, which include increase the stability of the polymer tothermal and/or light radiation. In this regard, the additives caninclude, but are not limited to, crosslinking agents, antioxidants,adhesion promoters, and the like. Non-limiting examples of suchcompounds are selected from the group consisting of the following,commercially available materials are indicated by such commercial names.

Advantageously, it has now been found that the compositions of thisinvention contain at least one or more of the crosslinking agents. Anyof the crosslinking agents known in the literature that would bringabout the crosslinking of the polymer with other additives when the baseis generated at a desirable temperature during the curing stage can beemployed in the embodiments of the present invention. Accordingly, insome embodiments of this invention, the photosensitive composition ofthis invention, without any limitation, contains one or more epoxycompounds selected from the following:

Other exemplary cross-linking or crosslinkable materials that can beused as additives in the forming of a photosensitive composition of thepresent invention include, among others, bisphenol A epoxy resin,bisphenol F epoxy resin, silicone containing epoxy resins or the like,propylene glycol diglycidyl ether, polypropylene glycol diglycidylether, glycidyloxypropyltrimethoxysilane, polymethyl(glycidyloxypropyl)cyclohexane or the like; polymers containingoxazoline rings such as 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline,1,3-bis(2-oxazoline-2-yl)benzene, 1,4-bis(2-oxazoline-2-yl)benzene,2,2′-bis (2-oxazoline), 2,6-bis(4-isopropyl-2-oxazoline-2-yl)pyridine,2,6-bis(4-phenyl-2-oxazoline-2-yl)pyridine, 2,2′-isopropylidenebis(4-phenyl-2-oxazoline), (S,S)-(−)-2,2′-isopropylidenebis(4-tert-butyl-2-oxazoline), poly(2-propenyl-2-oxazoline) or the like;N-methylolacrylamide, N-methylol methacrylamide, furfuryl alcohol,benzyl alcohol, salicyl alcohol, 1,2-benzene dimethanol, 1,3-benzenedimethanol, 1,4-benzene dimethanol and resole type phenol resin ormixtures thereof.

Any amount of epoxy compound can be employed in the photosensitivecomposition of this invention which brings about the desiredcrosslinking effect of the total composition. Generally, as noted above,such amount can range from 10 to 100 parts per hundred parts by mass(pphr) of the polymer, inclusive, as described herein. In some otherembodiments such amount can range from 15 to 80 pphr, inclusive. In someother embodiments such amount can range from 40 to 60 pphr, inclusive.In some embodiments one or more of the epoxy compound as describedherein is employed. In another embodiment at least two of the epoxycompounds are employed.

In another aspect of this invention there is further provided aphotoimageable composition comprising:

a) a polymer having one or more repeating units of formula (IA) derivedfrom a monomer of formula (I):

wherein

represents a position at which the bonding takes place with anotherrepeat unit;

R₁₈ is (C₆-C₁₈)alkyl; perfluoro(C₁-C₁₈)alkyl; (C₆-C₁₀)aryl(C₁-C₆)alkyl;—(CH₂)_(a)—C(CF₃)₂OR, —(CH₂)_(a)—CO₂R₂ where a is an integer from 0 to4, and R₂ is selected from hydrogen and (C₁-C₄)alkyl;

a group of formula (A):(CH₂)_(b)—(OCH₂—CH₂)_(c)—OR  (A); and

a group of formula (B):

wherein:

b is an integer from 0 to 10;

c is an integer 0, 1, 2, 3 or 4; and

R is hydrogen, linear or branched (C₁-C₆)alkyl, (C₅-C₈)cycloalkyl,(C₆-C₁₀)aryl or (C₇-C₁₂)aralkyl;

b) a photobase generator selected from the group consisting of: acompound of formula (IV), (V), (VI), (VIIA), (VIIB) and (VIIC) asdescribed hereinabove; and

c) a carrier solvent.

In this aspect of the invention, any of the polymer encompassing one ormore repeat units derived from the corresponding monomer of formula(VIII) can be used to form the composition embodiment of this invention.Specific examples of such monomer of formula (VIII), without anylimitation, can be selected from the group consisting of:

-   norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);-   trioxanonanenorbornene (NBTON);-   tetraoxadodecanenorbornene (NBTODD);-   5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM);-   5-(3-methoxypropanoxy)methyl-2-norbornene (NB-3-MPM);-   ethyl 3-(bicyclo[2.2.1]hept-2-en-2-yl)propanoate (EPEsNB);-   bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (Acid NB); and-   norbornenylpropanoic acid (NBEtCOOH).

In one of the embodiments encompassing this aspect of the invention thepolymer is derived from the following monomers of formula (VIII):

-   norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);    and-   norbornenylpropanoic acid (NBEtCOOH).

Again, any one or more of the specific PBGs as disclosed hereinabove canbe employed in this aspect of the composition embodiment of thisinvention without any limitation.

Further, this aspect of the composition embodiment of this inventionfurther contains one or more additives as described herein, includingparticularly a crosslinking agent, an antioxidant and an adhesionpromoter, and various other additives as described hereinabove.

In yet another aspect of this invention there is further provided amethod of forming a patterned film for the fabrication of amicroelectronic or optoelectronic device comprising:

coating a suitable substrate with a composition according to thisinvention to form a film;

patterning the film with a mask by exposing to a suitable radiation;

developing the film after exposure to form a photo-pattern; and

curing the film by heating to a suitable temperature.

The coating of the desired substrate to form a film with photosensitivecomposition of this invention can be performed by any of the coatingprocedures as described herein and/or known to one skilled in the art,such as by spin coating. Other suitable coating methods include withoutany limitation spraying, doctor blading, meniscus coating, ink jetcoating and slot coating. Suitable substrate includes any appropriatesubstrate as is, or may be used for electrical, electronic oroptoelectronic devices, for example, a semiconductor substrate, aceramic substrate, a glass substrate.

Next, the coated substrate is first softbaked before the curing, i.e.,heated to facilitate the removal of residual casting solvent, forexample to a temperature from 60° C. to 140° C. for from about 1 to 30minutes, although other appropriate temperatures and times can be used.In some embodiments the substrate is first softbaked at a temperature offrom about 100° C. to about 130° C. for 2 minutes to 10 minutes. Afterthe heating, the film is generally imagewise exposed to an appropriatewavelength of actinic radiation, wavelength is generally selected basedon the choice of the photobase generator employed in combination withthe photosensitizer, if any, in the polymer composition as describedhereinabove. However, generally such appropriate wavelength is thatproduced by a mercury vapor lamp which is from 200 to 450 nm dependingupon the type of mercury vapor lamp employed. It will be understood thatthe phrase “imagewise exposure” means exposing through a masking elementto provide for a resulting pattern of exposed and unexposed portion ofthe film.

After an imagewise exposure of the film formed from the composition inaccordance with the present invention, a development process isemployed. Advantageously, the compositions of this invention function as“positive tone” or “negative tone” compositions depending upon the typeof composition employed and the intended use thereof.

As is well known in the art, in the “positive tone” compositions, forexample, the development process removes only exposed portions of thefilm thus leaving a positive image of the masking layer in the film.That is, the film upon exposure to suitable actinic radiation becomesmore soluble in a developing solvent.

Generally, suitable developers for positive tone compositions caninclude aqueous solutions of inorganic alkalis such as sodium hydroxide,potassium hydroxide, sodium carbonate, ammonia, and aqueous solutions oforganic alkalis such as 0.26N tetramethylammonium hydroxide (TMAH),ethylamine, triethylamine and triethanolamine. Where an organic alkaliis used, generally an organic solvent essentially fully miscible withwater is used to provide adequate solubility for the organic alkali.Aqueous solutions of TMAH are well known developer solutions in thesemiconductor industry. Suitable developers can also include organicsolvents such as propylene glycol methyl ether acetate (PGMEA),2-heptanone, cyclohexanone, toluene, xylene, ethyl benzene, mesityleneand butyl acetate, among others.

Thus some embodiments of the present invention provide self-imageablefilms that after imagewise exposure, a resulting image is developedusing an aqueous base solution. After the image is developed, thesubstrate is rinsed to remove excess developer solvent, typical rinseagents are water or appropriate alcohols and mixtures thereof.

After the aforementioned rinsing, the substrate is dried and the imagedfilm finally cured. That is to say, the image is fixed. In this step,the photobase generator present in the unexposed region of thecomposition may thermally decompose to release the free base, whichfacilitates further cross-linking reaction of the remaining polymermaterial. The heating is generally carried out at a desirabletemperature, for example, from above 160° C. to 250° C. for a sufficientlength of time, i.e., from several minutes to one or more hours. Wherethe remaining layer cross links with the epoxy additive as describedherein. Advantageously, it has now been found that such a curing stepnot only helps in fixing the image, it also enhances thethermo-mechanical properties of the film.

Accordingly, in some embodiments the resulting imagewise film or layeris cured by heating the patterned and developed substrate at atemperature of from about 170° C. to about 220° C. for about 20 minutesto about 240 minutes. In some other embodiments such curing is carriedout at a temperature of from about 190° C. to about 210° C. for about 30minutes to about 180 minutes. In yet some other embodiments such curingis carried out at a temperature of from about 180° C. to about 200° C.for about 60 minutes to about 120 minutes. Finally, in some otherembodiments of this invention, the curing is performed at a temperatureof from about 130° C. to about 200° C. at an incremental heating ramp ofabout 5° C./minute and for about 1 to 3 hours. In some other embodimentsthe pattern reflow is completely absent after curing step, which meansthat pattern integrity is maintained, thus providing image resolution ofabout 10 μm. In some other embodiments the image resolution is about 5μm.

As noted above, advantageously, the compositions of this invention arealso useful as “negative tone” compositions, for example, thedevelopment process removes only unexposed portions of the film thusleaving a negative image of the masking layer in the film. That is, thefilm upon exposure to suitable actinic radiation becomes less soluble ina developing solvent, thus removing only the unexposed regions.

In general, the films formed from the negative tone compositions arefirst “image-wise” exposed to a suitable radiation, and then heated to atemperature of from about 120° C. to 150° C. for sufficient length oftime to ensure that the free base generated during exposure in theexposed regions aid in crosslinking the polymer with other additives.The unexposed regions remain essentially same. Then the films aredeveloped.

Generally, suitable developers for negative tone compositions of thisinvention are same as the developers used for “positive tone”compositions as described hereinabove. That is, any of the aqueoussolutions of inorganic alkalis, ammonia, and aqueous solutions oforganic alkalis such as 0.26N tetramethylammonium hydroxide (TMAH), andthe like can be used in combination with any of the organic solvents asdescribed hereinabove.

Thus some embodiments of the present invention provide self-imageablefilms that after imagewise exposure, a resulting image is developedusing an aqueous base solution, which removes the unexposed regions ofthe film. After the image is developed, the substrate is rinsed toremove excess developer solvent, typical rinse agents are water orappropriate alcohols and mixtures thereof.

After the aforementioned rinsing, the substrate is dried and the imagedfilm finally cured. That is to say, the image is fixed. The heating isgenerally carried out at a desirable temperature, for example, fromabove 160° C. to 250° C. for a sufficient length of time, i.e., fromseveral minutes to one or more hours. Where the remaining layer crosslinks with the epoxy additive as described herein. Advantageously, ithas now been found that such a curing step not only helps in fixing theimage, it also enhances the thermo-mechanical properties of the film asis apparent from the examples that follows.

Accordingly, in some embodiments the resulting imagewise film or layeris cured by heating the patterned and developed substrate at atemperature of from about 170° C. to about 220° C. for about 20 minutesto about 240 minutes. In some other embodiments such curing is carriedout at a temperature of from about 190° C. to about 210° C. for about 30minutes to about 180 minutes. In yet some other embodiments such curingis carried out at a temperature of from about 180° C. to about 200° C.for about 60 minutes to about 120 minutes. Finally, in some otherembodiments of this invention, the curing is performed at a temperatureof from about 130° C. to about 200° C. at an incremental heating ramp ofabout 5° C./minute and for about 1 to 3 hours. In some other embodimentsthe pattern reflow is completely absent after curing step, which meansthat pattern integrity is maintained, thus providing image resolution ofabout 10 μm. In some other embodiments the image resolution is about 5μm.

Advantageously, in some embodiments of this invention, it has also beenfound that the image resolution can be improved in the negative tonecompositions by tailoring the appropriate exposure dose. That is,depending upon the exposure dose used the image resolution is generallyimproved. Accordingly, in some embodiments the films are imagewiseexposed to a suitable radiation at a dosage level of from about 100mJ/cm² to 1000 mJ/cm². In some other embodiments the exposure dosageemployed is from about 200 mJ/cm² to 800 mJ/cm². In some otherembodiments the exposure dosage employed is at least about 250 mJ/cm².By employing suitable exposure dosage as described herein it is nowpossible to obtain films that exhibit lower degree of film loss afterexposure. That is, generally the exposed area film thickness loss orbright field loss (BFL) of the films that exhibit negative tone (NT)image is low as measured by the film thicknesses before and afterdevelopment in an exposed region of the film. Thus, in some embodimentsit has now been found that the BFL loss is less than 20% by exposing thefilm to a higher exposure dose. In some other embodiments the BFL lossis less than 10%. It has also been observed that by increasing theexposure dosage the sidewall angle of the image can be substantiallyincreased. That is, for example, the vias typically formed in thesemiconductor fabrications retain a very high sidewall angles. Thus, insome embodiments it has now been found that the side wall angle of theimage formed, for example vias, is at least 65°. In some otherembodiments the side wall angle of the image formed is at least 80°.

The devices are produced by using embodiments of the photosensitiveresin composition of the present invention to form layers which arecharacterized as having improved mechanical properties, high heatresistance, an appropriate water absorption rate, high transparency, andlow permittivity. In addition, such layers generally have anadvantageous coefficient of thermal elasticity (CTE) after curing, highelongation to break (ETB), low wafer stress, glass transitiontemperature (T_(g)) higher than 100° C., among other improved propertiesas apparent from the examples that follows.

As previously mentioned, exemplary applications for embodiments of thephotosensitive compositions in accordance with the present inventioninclude redistribution layer, die attach adhesive, wafer bondingadhesive, insulation films (interlayer dielectric layers), protectingfilms (passivation layers), mechanical buffer films (stress bufferlayers) or flattening films for a variety of semiconductor devices,including printed wiring boards. Specific applications of suchembodiments encompass a die-attach adhesive to form a single ormultilayer semiconductor device, dielectric film which is formed on asemiconductor device; a buffer coat film which is formed on thepassivation film; an interlayer insulation film which is formed over acircuit formed on a semiconductor device.

Advantageously, it has now been found that the photosensitivecompositions of this invention may be useful to form adhesive layers forbonding the semiconductor chips to each other, such as in chip-stackapplications. For example, a redistribution layer used for such apurpose is composed of a cured product of the photosensitive adhesivecomposition of the present invention. Surprisingly, it has now beenfound that although the adhesive layer is a single-layer structure, itnot only exhibits sufficient adhesiveness to the substrate but also isfree of significant stress resulting due to the curing step.Accordingly, it may now be possible to avoid undesirably thick layer offilm encompassing the chip as a laminate. It has been further observedthat the laminates formed in accordance with the present invention arereliable in that the relaxation of stress concentration between layerscaused by thermal expansion difference or the like can be obtained. As aresult, the semiconductor device having low height and high reliabilitycan be obtained. That is, devices with low aspect ratio and lowthickness can be obtained. Such semiconductor device becomesparticularly advantageous to electronic equipment, which has very smallinternal volume and is in use while carrying as a mobile device, forexample. Even more advantageously, by practice of this invention it maynow be possible to form a variety of electronic devices featuringhitherto unachievable level of miniaturization, thinning andlight-weight, and the function of the semiconductor device is not easilydamaged even if such devices are subject to rugged operations such asswinging or dropping.

Accordingly, in some of the embodiments of this invention there is alsoprovided a cured product obtained by curing the photosensitivecomposition as described herein. In another embodiment there is alsoprovided an optoelectronic or microelectronic device comprising thecured product of this invention as described herein.

The following examples are detailed descriptions of methods ofpreparation and use of certain compounds/monomers, polymers andcompositions of the present invention. The detailed preparations fallwithin the scope of, and serve to exemplify, the more generallydescribed methods of preparation set forth above. The examples arepresented for illustrative purposes only, and are not intended as arestriction on the scope of the invention. As used in the examples andthroughout the specification the ratio of monomer to catalyst is basedon a mole to mole basis.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:

NB—bicyclo[2.2.1]hept-2-ene; PENB—5-phenethylbicyclo[2.2.1]hept-2-ene;HFANB—norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol;NBEtCOOH—norbornenylpropanoic acid;DecNB—5-decylbicyclo[2.2.1]hept-2-ene; MA—maleic anhydride;PBG-1—1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethylcyclohexylcarbamate; PBG-2—2-nitrobenzyl4-hydroxypiperidine-1-carboxylate; PBG-3—4,5-dimethoxy-2-nitrobenzyl2,6-dimethylpiperidine-1-carboxylate;PBG-4—2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one;PBG-5—2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one;PBG-6—3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidin-1-ium2-(3-benzoylphenyl)propanoate;PBG-7—1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl1H-imidazole-1-carboxylate; PBG-8—guanidinium2-(3-benzoylphenyl)propionate;PBG-9—(Z)—N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propan-2-aminium2-(3-benzoylphenyl)propanoate;TMPTGE—2,2′-(((2-ethyl-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxirane);GE-36—triglycidyl ether of poly(oxypropylene)epoxide ether of glycerol;BY16-115—silicone modified epoxy compound; EPON862—bis(4-(oxiran-2-ylmethoxy)phenyl)methane;Si-75—((triethoxysilyl)propyl)disulfide;3-GTS—triethoxy(3-(oxiran-2-ylmethoxy)propyl)silane, also commonly knownas 3-glycidoxypropyl triethoxysilane;CPTX—1-chloro-4-propoxy-1,9a-dihydro-9H-thioxanthen-9-one;KBM-403—3-glycidoxypropyl trimethoxysilane;Naugard-445—bis(4-(2-phenylpropan-2-yl)phenyl)amine;AO-80—2,2′-((2-hydroxy-5-methyl-1,3-phenylene)bis(methylene))bis(4-methylphenol);SIT-7908.0—diethoxy(propoxy)(3-thiocyanatopropyl)silane; MegafaceF-556—oligomer with fluoro, hydrophilic and lipophilic group from DICCorp.; GBL—γ-butyrolactone; PGMEA—propylene glycol methyl ether acetate;PBG—photobase generator; ROMA—ring opened maleic anhydride polymer withan alcohol; ROMI—ring opened maleic anhydride polymer with an amine;phr—parts per hundred parts resin; R. T.—room temperature; LC-MS: liquidchromatography-mass spectroscopy; GPC: gel permeation chromatography;M_(w)—weight average molecular weight; PDI—polydispersity index; phr:parts per hundred parts of resin.

The following examples describe the procedures used for the preparationof various polymers as disclosed herein in the preparation of thecompositions of this invention. However, it should be noted that theseexamples are intended to illustrate the disclosure without limiting thescope thereof.

Polymer Examples

The polymers used to form the photosensitive compositions of thisinvention are generally known in the literature and are prepared inaccordance with the well-known literature procedures. See for example,the U.S. Pat. No. 8,715,900 for all synthetic procedures related to ROMApolymers and the copending U.S. patent application Ser. No. 14/477,928,filed Sep. 5, 2014 for all synthetic procedures related to ROMApolymers. Other polymers as used herein can be made in accordance withany of the other literature procedure as described particularly in U.S.Pat. Nos. 5,929,181; 6,455,650; 6,825,307; and 7,101,654.

Photoimageable Polymer Composition and Imaging Studies

The following Examples illustrate the imageability of the compositionsof this invention with a variety of other components as describedherein.

Example 1

A fully ring opened copolymer having the monomer composition of 50:50molar ratio of PENB/MA ring opened with methanol (M_(w) 8,500 and PDI1.9, repeat units of formula (IIIA) where Z is O and R₇ is methyl) (100parts resin) was dissolved in GBL (120 parts) having the specificamounts of additives, expressed as parts per hundred resin (pphr) PBG-4(7.5 phr), CPTX (1 phr) as photosensitizer, TMPTGE (10 phr) and GE-36(50 phr) as crosslinking agents, AO-80 (5 phr) as an anti-oxidant,Naugard-445 (5 phr), Megaface F-556 (0.3 phr) and SIT-7908.0 (3 phr)were mixed in an appropriately sized amber HDPE bottle. The mixture wasrolled for 18 hours to produce a homogeneous solution. Particlecontamination was removed by filtering the polymer solution through a0.45 μm pore polytetrafluoroethylene (PTFE) disc filter under 35 psipressure, the filtered polymer solution was collected in a low particleHDPE amber bottle and the resulting solution stored at 5° C.

Examples 2-19

Example 1 was substantially repeated in these Examples 2-19 except thatthe type of polymer and other additives were varied as summarized inTables 1 to 5. GBL was used as the solvent in all of the Examples 2-19except in Examples 8A through 8D and Example 11 the solvent employed wasPGMEA. In Examples 15 to 18, 230 parts of GBL was used and in Example 19180 parts of GBL was used.

TABLE 1 Ingredients Example 2 Example 3 Example 4 Example 5 Example 14Polymer - Amount 100 phr 100 phr 100 phr 100 phr 100 phr Polymer - TypePENB/ROMA- PENB/ROMA- PENB/ROMA- PENB/ROMA- PENB/ROMA- MeOH MeOH MeOHMeOH MeOH PBG-4 7.5 phr 7.5 phr 5 phr 5 phr 7.5 phr CPTX 1 phr 1 phr 1phr 1 phr 1 phr TMPTGE 10 phr 10 phr 25 phr — — BY16-115 — — — 25 phr —GE-36 50 phr 50 phr 25 phr 25 phr 50 phr AO-80 5 phr 5 phr 5 phr 5 phr 5phr Naugard 445 5 phr 5 phr 5 phr 5 phr 5 phr Megaface F-556 0.2 phr 0.3phr — — 0.3 phr SIT-7908.0 3 phr 3 phr 3 phr 3 phr 3 phr

TABLE 2 Ingredients Example 6 Example 7 Polymer - Amount 100 phr 100 phrPolymer - Type PENB/ROMA-MeOH PENB/ROMA-MeOH PBG-4 5 phr 5 phr CPTX — 1phr TMPTGE 40 phr 40 phr

TABLE 3 Example Example Example Example Ingredients 8A 8B 8C 8DPolymer - 100 phr 100 phr 100 phr 100 phr Amount Polymer - PENB/ PENB/PENB/ PENB/ Type ROMA- ROMA- ROMA- ROMA- MeOH MeOH MeOH MeOH PBG PBG-1,PBG-2, PBG-3, PBG-4, 5 phr 5 phr 5 phr 5 phr CPTX 1 phr 1 phr 1 phr 1phr TMPTGE 40 phr 40 phr 40 phr 40 phr Megaface 0.15 phr 0.15 phr 0.15phr 0.15 phr F-556 SIT-7908.0 3 phr 3 phr 3 phr 3 phr

TABLE 4 Ingre- Example Example Example Example Example dients 9 10 11 1213 Polymer - 100 phr 100 phr 100 phr 100 phr 100 phr Amount Polymer -NB/ HFANB/ PENB/ Sty/ PENB/ Type ROMA- NBEtCOOH ROMA- ROMI- ROMA- BuOHMeOH BuNH₂ MeOH PBG PBG-4 PBG-4 PBG-6 PBG-4 PBG-5 PBG 5 phr 5 phr 5 phr10 phr 7.6 phr CPTX 1 phr 1 phr 1 phr — — TMPTGE 40 phr 40 phr 40 phr 40phr 10 phr GE-36 — — — — 50 phr Megaface 0.15 phr 0.15 phr 0.15 phr —0.3 phr F-556 SIT- 3 phr 3 phr 3 phr — 3 phr 7908.0

TABLE 5 Ingredients Example 15 Example 16 Example 17 Example 18 Example19 Polymer - Amount 100 phr 100 phr 100 phr 100 phr 100 phr Polymer -Type DecNB/PENB/ DecNB/PENB/ DecNB/PENB/ DecNB/PENB/ DecNB/PENB/ (molarratio) ROMA-MeOH ROMA-MeOH ROMA-MeOH ROMA-MeOH ROMA-MeOH (20/30/50)(20/30/50) (20/30/50) (20/30/50) (20/30/50) PBG PBG-7 PBG-8 PBG-2 PBG-9PBG-4 PBG 7.5 phr 7.5 phr 7.5 phr 7.5 phr 5 phr CPTX 2.5 phr 2.5 phr 2.5phr 2.5 phr 1.5 phr EPON-862 20 phr 20 phr 20 phr 20 phr 20 phr GE-36 30phr 30 phr 30 phr 30 phr 30 phr 3-GTS 3 phr 3 phr 3 phr 3 phr 3 phr

The polymer as used in the above Tables 1 to 5, PENB/ROMA-MeOH meansthat it is a 50:50 molar ratio of PENB/MA ring opened with methanol(M_(w) 8,500, PDI 1.9, repeat units of formula (IIIA) where Z is O andR₇ is methyl). Similarly, NB/ROMA-BuOH means that it is a 50:50 molarratio of NB/MA ring opened with n-butanol (M_(w) 12,500, PDI 2.1, repeatunits of formula (IIIA) where Z is O and R₇ is n-butyl); Sty/ROMI-BuNH₂means that it is a 75:25 molar ratio of styrene/MA ring opened withn-butyl amine (M_(w) 22,600, PDI 2, repeat units of formula (IIIA) whereZ is N-n-butyl and R₇ is hydrogen); DecNB/PENB/ROMA-MeOH is a terpolymerof 20/30/50 molar ratio where MA units are ring opened with methanol(M_(w) 14,500, PDI 1.9); and HFANB/NBEtCOOH is a 75:25 molar ratiocopolymer of HFANB and NBEtCOOH (M_(w) 125,000, PDI 2.3).

Example 20 Spin Coating Procedure

Compositions thus formed in Examples 1-18 were brought to roomtemperature and each of which were applied to thermal oxide siliconwafers by spin coating first at 500 rpm for 10 seconds followed by aselected spin speed for 30 seconds as further described below.

Example 21 Post Apply Bake Procedure (PAB)

The substrates produced in accordance with the procedures of Example 19were then placed on a hot plate at selected temperature for a sufficientlength of time as further described in the following examples to obtaina polymer film.

Example 22 Photo Imaging Procedures

Each polymer film was then imagewise exposed through a broad bandHg-vapor light source (at 365 nm using a band pass filter) either usinga patterned mask or without a mask at an effective dose as described inthe following examples.

Example 23 Post Exposure Bake (PEB) Procedures

A few of the photo exposed films from Example 22 were then post exposurebaked on a hot plate at a selected temperature for a selected time asfurther described in the following examples.

Example 24 Aqueous Base Developing Procedure

Each film after exposure in accordance with procedures of Example 22 andsome film samples after PEB procedures in accordance of procedures asset forth in Example 23 were developed as follows. The exposedsubstrates and in some cases exposed and post exposure baked substrateswere immersed in developer (2.38 wt. % TMAH) for various times(immersion development). The unexposed area film thickness loss or darkfield loss (DFL) of the films that exhibit positive tone (PT) imagedevelopment is determined by measuring the film thicknesses before andafter development in an unexposed region of the film and reported aspercent loss of the film thickness in areas of the film that is notexposed to the radiation. The exposed area film thickness loss or brightfield loss (BFL) of the films that exhibit negative tone (NT) imagedevelopment is determined by measuring the film thicknesses before andafter development in an exposed region of the film and reported aspercent loss of the film thickness in areas of the film that is exposedto the radiation.

Example 25 Dissolution Rate Measurements

The film thicknesses of the coated films were measured using a profilerbefore and after immersion in an aqueous base developer (2.38 wt. %TMAH). The dissolution rates were calculated based on the measured filmthickness loss and the time of immersion to the developer.

Example 26 Curing Procedures

The spin coated film samples were baked, as needed, in an oven undernitrogen atmosphere in order to further remove any residual solvents andto thermally cure the films at 180° C. for 2 hours. These cured filmswere used to measure their thermo-mechanical properties, such as waferstress, Young's modulus, tensile strength (TS), elongation to break(ETB), glass transition temperature (T_(g)), coefficient of thermalexpansion (CTE), thermal decomposition temperatures, thermal cyclingtest (TCT), thermo-oxidative stability test (TOS), adhesion to Si,adhesion to Cu and pattern flow.

The following Examples 26 to 33 illustrate the photo-imageability of thecompositions of this invention.

Example 27

The composition of Example 1 was spin coated on a 4-inch thermal oxidesilicon wafer at 1400 rpm for 30 seconds and post apply baked (PAB) at110° C. for 3 minutes to obtain a film of 10.5 μm thickness. The filmwas then exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of327 mJ/cm². It was then post exposure baked (PEB) at 140° C. for 5minutes resulting in a film thickness of 10.2 μm. After developing for45 seconds in 2.38 wt. % TMAH the film thickness in the exposed regiondecreased to 8.1 μm and the film of the unexposed regions werecompletely removed forming a negative tone image. It is evident from theoptical micrograph images taken top-down the 10 μm trenches and 20 μmline patterns were clearly observed. The calculated bright field loss(BFL) was 21%.

Example 28

The composition of Example 2 was spin coated on a 4-inch thermal oxidesilicon wafer at 1300 rpm for 30 seconds and post apply baked (PAB) at120° C. for 3 minutes to obtain a film of 9.7 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of350 mJ/cm². It was then post exposure baked (PEB) at 140° C. for 5minutes resulting in a film thickness of 9.1 μm. After developing for 50seconds in 2.38 wt. % TMAH the film thickness in the exposed regionslightly increased to 9.3 μm and the film of the unexposed regions werecompletely removed forming a negative tone image. It is evident from theoptical micrograph images taken top-down the 10 μm trenches and 20 μmline patterns were clearly observed. The calculated bright field loss(BFL) was −2% indicating the film thickness gain of 2% in the exposedregion.

Example 29

The composition of Example 4 was spin coated on a 4-inch thermal oxidesilicon wafer at 1100 rpm for 30 seconds and post apply baked (PAB) at120° C. for 3 minutes to obtain a film of 10.1 μm thickness. The filmwas then exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of400 mJ/cm². It was then post exposure baked (PEB) at 135° C. for 5minutes resulting in a film thickness of 9.8 μm. After developing for120 seconds in 2.38 wt. % TMAH the film thickness in the exposed regionslightly decreased to 9.4 μm and the film of the unexposed regions werecompletely removed forming a negative tone image. It is evident from theoptical micrograph images taken top-down the 10 μm trenches and 20 μmline patterns were clearly observed. The calculated bright field loss(BFL) was 4%.

FIG. 1 shows the SEM photograph of 22.8 μm space and 30.9 μm linesformed by the negative tone photo-imaging evidencing high quality imagescan be obtained by the compositions of this invention.

Example 30

The composition of Example 9 was spin coated on a 4-inch thermal oxidesilicon wafer at 4000 rpm for 30 seconds and post apply baked (PAB) at100° C. for 3 minutes to obtain a film of 1.8 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of327 mJ/cm². It was then post exposure baked (PEB) at 120° C. for 2minutes. After developing for 30 seconds in 2.38 wt. % TMAH the filmthickness in the exposed region decreased to 1.4 μm and the film of theunexposed regions were completely removed forming a negative tone image.It is evident from the optical micrograph images taken top-down the 3 μmlines, 10 μm pillars and 50 μm contact hole patterns were clearlyobserved. The calculated bright field loss (BFL) was 21%.

Example 31

The composition of Example 10 was spin coated on a 4-inch thermal oxidesilicon wafer at 3000 rpm for 30 seconds and post apply baked (PAB) at100° C. for 2 minutes to obtain a film of 2.7 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of510 mJ/cm². It was then post exposure baked (PEB) at 115° C. for 4minutes. After developing for 35 seconds in 2.38 wt. % TMAH the filmthickness in the exposed region decreased to 2.2 μm and the film of theunexposed regions were completely removed forming a negative tone image.It is evident from the optical micrograph images taken top-down the 3 μmlines, 10 μm pillars and 50 μm contact hole patterns were clearlyobserved. The calculated bright field loss (BFL) was 18%.

Example 32

The composition of Example 11 was spin coated on a 4-inch thermal oxidesilicon wafer at 2000 rpm for 30 seconds and post apply baked (PAB) at100° C. for 2 minutes to obtain a film of 1.6 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of791 mJ/cm². It was then post exposure baked (PEB) at 120° C. for 3minutes. After developing for 105 seconds in 2.38 wt. % TMAH the filmthickness in the exposed region decreased to 0.1 μm and the film of theunexposed regions were completely removed forming a negative tone image.The calculated bright field loss (BFL) was 94%.

Example 33

The composition of Example 12 was spin coated on a 4-inch thermal oxidesilicon wafer at 700 rpm for 30 seconds and post apply baked (PAB) at110° C. for 2 minutes to obtain a film of 13 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of800 mJ/cm². After developing for 7 seconds in 2.38 wt. % TMAH the filmthickness in the unexposed region decreased to 8.7 μm and the film ofthe exposed regions were completely removed forming a positive toneimage. The calculated dark field loss (DFL) was 33%.

FIG. 2 shows the SEM photograph where a 7.8 μm space is clearly visible,thus evidencing that the compositions of this invention can readily betailored to form positive tone images.

Example 34

The composition of Example 13 was spin coated on a 4-inch thermal oxidesilicon wafer at 1000 rpm for 30 seconds and post apply baked (PAB) at100° C. for 3 minutes to obtain a film of 9.8 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of644 mJ/cm². It was then post exposure baked (PEB) at 140° C. for 3minutes. After developing for 40 seconds in 2.38 wt. % TMAH the filmthickness in the exposed region decreased to 8.6 μm and the film of theunexposed regions were completely removed forming a negative tone image.It is evident from the optical micrograph images taken top-down the 2 μmline pattern formations were clearly observed. The calculated brightfield loss (BFL) was 6%.

Example 35

The composition of Example 17 was spin coated on a 4-inch thermal oxidesilicon wafer at 1000 rpm for 30 seconds and post apply baked (PAB) at100° C. for 3 minutes to obtain a film of 9.2 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of1000 mJ/cm². It was then post exposure baked (PEB) at 140° C. for 3minutes. After developing for 60 seconds in 2.38 wt. % TMAH the filmthickness in the exposed region slightly decreased to 8.3 μm and thefilm of the unexposed regions were completely removed forming a negativetone image. It is evident from the optical micrograph images takentop-down the 25 μm line and 100 μm via patterns were clearly observed.The calculated bright field loss (BFL) was 9%.

Example 36

The composition of Example 19 was spin coated on a 5-inch thermal oxidesilicon wafer at 1800 rpm for 30 seconds and post apply baked (PAB) at100° C. for 3 minutes to obtain a film of 9.6 μm thickness. The film wasthen exposed using a patterned mask to a broad band Hg-vapor lightsource (at 365 nm using a band pass filter) and at an exposure dose of405 mJ/cm². It was then post exposure baked (PEB) at 120° C. for 5minutes. After developing for 25 seconds in 2.38 wt. % TMAH the filmthickness in the exposed region decreased to 7.9 μm and the film of theunexposed regions were completely removed forming a negative tone image.It is evident from the optical micrograph images taken top-down the 10μm line and 25 μm via patterns were clearly observed. The calculatedbright field loss (BFL) was 18%.

Dissolution Rate Measurements

The following Examples 37 and 38 illustrate the procedures to measurethe dissolution rate of the compositions of this invention todemonstrate positive tone or negative tone behaviors.

Example 37

The composition of Example 6 was spin coated on a 4-inch thermal oxidesilicon wafer at 2000 rpm for 30 seconds and post apply baked (PAB) at130° C. for 3 minutes. The wafer was cleaved into two parts. Thedissolution rate of one part of this film was measured by the immersionin 2.38 wt. % TMAH and measuring the film thicknesses before and afterTMAH immersion. The measured dissolution rate was 215 nm/sec. The otherpart of the film was first exposed to a blanket exposure dose of 1 J/cm²(EXD) and then its dissolution rate was measured similarly, whichincreased to 536 nm/sec indicating a positive tone (PT) behavior. Thatis, the exposed areas became more soluble upon exposure to a radiation.

The same formulation was spin coated at 2000 rpm for 30 seconds on a4-inch thermal oxide silicon wafer and post apply baked at 130° C. for 3minutes and cleaved to two parts. One part was further baked at 130° C.for 3 minutes to mimic the post exposure bake (PEB) condition. Thedissolution rate of this film was 100 nm/sec. The other part of thisfilm was exposed to a radiation dose of 1 J/cm² (EXD). Then this exposedpart was post exposure baked at 130° C. for 3 minutes (PEB), and thedissolution rate was measured, which was significantly decreased and had1% swelling of the film thickness indicating a negative tone (NT)behavior.

Example 38

The composition of Example 7 was spin coated at 2000 rpm for 30 secondson a 4-inch thermal oxide silicon wafer and post apply baked at 130° C.for 3 minutes and cleaved into two parts. The first part was furtherbaked at 130° C. for 3 minutes to mimic the post exposure bake (PEB)condition. The dissolution rate of this film was 61 nm/sec. The secondpart of this film was exposed to 1 J/cm² dose (EXD). The exposed partwas then post exposure baked at 130° C. for 3 minutes (PEB), and itsdissolution rate was measured similarly, which was significantlydecreased and had 6% swelling of the film thickness indicating anegative tone (NT) behavior.

Example 39

Two samples each from the composition of Examples 8A to 8D were spincoated as follows: one at 1000 rpm for 30 seconds on thermal oxidesilicon wafer to obtain a film thickness of about 2 μm and the secondone at 2000 rpm for 30 seconds to obtain a film thickness of about 1.5μm. All of these film samples were post apply baked at 100° C. for 3minutes. The film thicknesses (FT) of the films were measured and thenexposed to 510 mJ/cm² exposure dose. The exposed films were postexposure baked (PEB) at various temperatures for 5 minutes and immersedinto 2.38% TMAH, rinsed with water, air dried and their film thicknessesmeasured. The results, including the initial FT, PEB temperatureemployed in each sample, develop time, final FT and percent FT retentionare summarized in Table 6. It is evident from the data presented inTable 6 that the film thicknesses retained in various amounts indicatingthe degree of photo cross linking. The PBG-4 has the best photo crosslinking ability among the four photobase generators tested.

TABLE 6 Example Initial FT, Develop Final FT, % FT No. PBG μm PEB, ° C.time, sec μm retention 8A PBG-1 2.13 130 37 0 0 8A PBG-1 1.46 135 300.07 5 8B PBG-2 2.06 130 15 0.51 25 8B PBG-2 1.46 135 30 0.81 55 8CPBG-3 2.14 130 15 1.13 53 8C PBG-3 1.42 135 30 0.85 60 8D PBG-4 2.12 130120 1.96 92 8D PBG-4 1.51 125 80 1.32 87

The following Example 40 illustrates the shelf life stability of thecompositions of this invention.

Example 40

The viscosity of the composition from Example 3 was monitored for 14days at room temperature. The viscosity changed as follows; day-0, 340cps; day-6, 323 cps; day-9, 317 cps; day-14, 358 cps. According to theseresults the viscosity of the formulation kept at room temperatureincreased only about 5% in two weeks demonstrating the compositions ofthis invention are quite stable at room temperature.

The following Example 41 further demonstrates that the compositions ofthis invention exhibit good thermo-mechanical properties, such asYoung's modulus, wafer stress, tensile strength (TS), ETB, CTE andT_(g), among others, as summarized in Table 7.

Example 41

The composition Examples 1 to 5 and Example 14 were spin coated onto a5-inch bare silicon wafers to obtain films in the thickness range from9-13 μm. These films were exposed to a radiation at a dosage level from500-1000 mJ/cm² and post exposure baked at 130-140° C. range to 3-5minutes. These films were cured in an oven under nitrogen atmosphere at180° C. for 2 hours. Then various thermo-mechanical properties of thesefilms were measured as summarized in Table 7. It is evident from theseresults that the films obtained from the compositions of this inventionexhibit low wafer stress and high elongation to break, among variousother improved properties as summarized in Table 7.

TABLE 7 Example Example Example Example Example Example Property 1 2 3 45 14 TCT Pass — — Pass Pass — TOS — — Pass — — — Adhesion to Si — — PassPass — — Adhesion to Cu — — Pass Pass — — Young's 1.1 ± 0.1  1.4 ± 0.01 1.1 ± 0.04 2.3 ± 0.1 2.0 ± 0.1 0.98 ± 0.08 Modulus (GPa) TensileStrength  19 ± 2   26 ± 2  21 ± 5  43 ± 3  36 ± 6  18 ± 2  (MPa) ETB (%)14 ± 15 35 ± 15 24 ± 5  5 ± 2 4 ± 3 4 ± 1 CTE (ppmK⁻¹) 200 175 130 — 60— Wafer stress 4 ± 3 4 ± 2 3 ± 2 17 8 ± 1 5 ± 3 (MPa) T_(g) (° C.) 122119 156 144 —

The following Examples 42 and 43 illustrate the use of differentexposure dosage to improve the quality of the images obtained therefrom.

Examples 42-43

The composition of Example 19 was used in Example 42. The composition ofExample 4 was substantially used in Example 43 with the exception ofemploying 20 phr of TMPTGE and 30 phr of GE-36 as crosslinking agents.

Each of the compositions were then spin coated on a 4-inch thermal oxidesilicon wafer substantially using the procedures as set forthrespectively in Examples 29 and 36. The wafers were post apply baked(PAB) at 120° C. for 3 minutes. The films were then exposed using apatterned mask to a broad band Hg-vapor light source (at 365 nm using aband pass filter) and each film was exposed at different exposuredosages (EXD, mJ/cm²), as summarized in Table 8. Each of the exposedfilms were then post exposure baked (PEB) at 140° C. for 5 minutes anddeveloped as described in Examples 29 and 36. Then SEM photographs weretaken of each of the exposed film. The measured bright filed loss (BFL)for each of the films formed and the measured sidewall angles of 75 μmvias are summarized in Table 9. It is evident from this data thatsidewall angle and film loss improve with higher exposure energy.

FIGS. 3A to 3C show the SEM micrographs of a cross section of 75 μm viasobtained with the composition of Example 42. It is very clear from thesemicrographs that increasing the exposure energy dosage from 150 mJ/cm²to 400 mJ/cm², the bright field film loss (BFL) decreased substantiallyfrom 38% to 10%, and at the same time the sidewall angle steadilyincreased from 53° to 68°. Similar results are obtained for thecomposition of Example 43 as evidenced by the SEM micrographs shown inFIGS. 4A to 4C. By increasing the exposure dosage from 100 mJ/cm² to 300mJ/cm² the measured BFL decreased from 17% to 7% for FIGS. 4A to 4C. Theside wall angle was also increased substantially from 25° to 82°, thusevidencing that the exposure doses (EXD) of the compositions of thisinvention can readily be tailored to increase the side wall angles anddecrease the degree of film loss.

TABLE 9 EXD, Example 42 Example 43 mJ/cm² BFL, % Side wall angle BFL, %Side wall angle 100 — — 17   25° 150 38 53° — — 200 — — 8.3 57° 250 2158° — — 300 — — 7.2 82° 400 10 68° — —

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A photoimageable composition consisting of: a) acopolymer or terpolymer consisting of one or more first repeating unitsrepresented by formula (IA), said first repeating unit is derived from amonomer of formula (I):

wherein: m is 0; R₁, R₂, R₃ and R₄ are the same or different and eachindependently selected from the group consisting of hydrogen, hexyl,decyl, —(CH₂)₂—C(CF₃)₂OH, —(CH₂)₂—CO₂H, benzyl and phenethyl; and athird repeating unit selected from the group consisting of a repeat unitof formula (IIIA) and a repeat unit of formula (IIIB), said thirdrepeating unit is derived from a monomer of formula (III):

wherein: Z is O or N—R₁₂ wherein R₁₂ is selected from the groupconsisting of hydrogen, linear or branched (C₁-C₉)alkyl,(C₃-C₇)cycloalkyl and (C₆-C₁₂)aryl; R₅, R₆ and R₇ are each independentlyof one another selected from the group consisting of hydrogen, linear orbranched (C₁-C₉)alkyl, fluorinated or perfluorinated(C₁-C₉)alkyl,(C₆-C₁₂)aryl and (C₆-C₁₂)aryl(C₁-C₁₂)alkyl; and wherein each ofaforementioned groups, where valence is permissible, is optionallysubstituted with one or more groups selected from the group consistingof linear or branched (C₁-C₆)alkyl, (C₃-C₇)cycloalkyl,(C₁-C₆)perfluoroalkyl, (C₁-C₆)alkoxy, (C₃-C₇)cycloalkoxy,(C₁-C₆)perfluoroalkoxy, halogen, hydroxy, linear or branchedhydroxy(C₁-C₆)alkyl, acetoxy, phenyl, hydroxyphenyl and acetoxyphenyl;b) a photobase generator selected from the group consisting of: acompound of formula (IV):

a compound of formula (V):

a compound of formula (VI):

a compound of formula (VIIA):

a compound of formula (VIIB):

  a compound of formula (VIIC):

wherein R₁₃ and R₁₄ each independently of each other selected from thegroup consisting of hydrogen, linear or branched (C₁-C₈)alkyl,cyclohexyl, and (C₆-C₁₀)aryl; or R₁₃ and R₁₄ taken together with thenitrogen atom to which they are attached form a 5 to 7 memberedmonocyclic ring or 6 to 12 membered bicyclic ring, said rings optionallycontaining one or more heteroatoms selected from O and N, and said ringsoptionally substituted with a group selected from the group consistingof linear or branched (C₁-C₈)alkyl, (C₆-C₁₀)aryl, halogen, hydroxy,linear or branched (C₁-C₈)alkoxy and (C₆-C₁₀)aryloxy; and R₁₅, R₁₆ andR₁₇ are the same or different and each independently of one anotherselected from the group consisting of hydrogen, linear or branched(C₁-C₁₆)alkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₃)alkyl, hydroxy, halogen,linear or branched (C₁-C₁₂)alkoxy and (C₆-C₁₀)aryloxy; and c) a carriersolvent.
 2. The composition of claim 1, wherein Z is O, R₅ and R₆ arehydrogen, and R₇ is hydrogen or linear or branched (C₁-C₉)alkyl.
 3. Thecomposition of claim 1, wherein Z is N—R₁₂, R₅ and R₆ are hydrogen, R₇is hydrogen and R₁₂ is hydrogen or linear or branched (C₁-C₉)alkyl. 4.The composition of claim 1, wherein m=0, R₁, R₂, R₃ and R₄ are the sameor different and each independently selected from the group consistingof hydrogen, decyl, phenethyl, —(CH₂)₂—C(CF₃)₂OH and —(CH₂)₂—CO₂H. 5.The composition of claim 1, wherein the polymer consisting of: one ormore first repeat units derived from the corresponding monomers selectedfrom the group consisting of: bicyclo[2.2.1]hept-2-ene;5-decylbicyclo[2.2.1]hept-2-ene;norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol;5-phenethylbicyclo[2.2.1]hept-2-ene; and norbornenylpropanoic acid; andone or more third repeat units derived from the corresponding monomersselected from the group consisting of: maleic anhydride; and2-methyl-maleic anhydride.
 6. The composition of claim 1, wherein thepolymer is: a copolymer containing repeating units derived from5-phenethylbicyclo[2.2.1]hept-2-ene and ring opened maleic anhydriderepeat units which is ring opened with methanol.
 7. The composition ofclaim 1, wherein the polymer is: a copolymer containing repeating unitsderived from bicyclo[2.2.1]hept-2-ene and ring opened maleic anhydriderepeat units which is ring opened with n-butanol.
 8. The composition ofclaim 1, wherein the polymer is: a terpolymer containing repeating unitsderived from 5-phenethylbicyclo[2.2.1]hept-2-ene,5-decylbicyclo[2.2.1]hept-2-ene and ring opened maleic anhydride repeatunits which is ring opened with methanol.
 9. The composition of claim 1,wherein the photobase generator is a compound of formula (IV):

wherein R₁₃ and R₁₄ each independently of each other selected from thegroup consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl andphenyl; and R₁₅, R₁₆ and R₁₇ are the same or different and eachindependently of one another selected from the group consisting ofhydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxyand isopropoxy.
 10. The composition of claim 1, wherein the photobasegenerator is a compound of formula (V):

wherein R₁₃ and R₁₄ each independently of each other selected from thegroup consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl andphenyl; or R₁₃ and R₁₄ taken together with the nitrogen atom to whichthey are attached form a five or six membered monocyclic ring, and saidring is optionally substituted with a group selected from the groupconsisting of methyl, ethyl and hydroxy; and R₁₅, R₁₆ and R₁₇ are thesame or different and each independently of one another selected fromthe group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl,methoxy, ethoxy, n-propoxy and isopropoxy.
 11. The composition of claim1, wherein the photobase generator is a compound of formula (VI):

wherein R₁₃ and R₁₄ each independently of each other selected from thegroup consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl,cyclohexyl and phenyl; or R₁₃ and R₁₄ taken together with the nitrogenatom to which they are attached form a five or six membered monocyclicring; and R₁₅, R₁₆ and R₁₇ are the same or different and eachindependently of one another selected from the group consisting ofhydrogen, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxyand isopropoxy.
 12. The composition of claim 1, wherein the photobasegenerator is selected from the group consisting of: a compound offormula (VIIA):

a compound of formula (VIIB):

and a compound of formula (VIIC):


13. The composition of claim 1, wherein the photobase generator isselected from the group consisting of:


14. The composition of claim 1, wherein the photobase generator isselected from the group consisting of:


15. The composition of claim 1, wherein the photobase generator isselected from the group consisting of:


16. The composition of claim 1, wherein the photobase generator is: acompound of formula (VIIA):


17. The composition of claim 1, wherein the photobase generator is: acompound of formula (VIIB):


18. The composition of claim 1, wherein the photobase generator is: acompound of formula (VIIC):